US4454112A - Sunscreen composition containing tocopherol acetylsalicylate - Google Patents

Sunscreen composition containing tocopherol acetylsalicylate Download PDF

Info

Publication number
US4454112A
US4454112A US06/358,557 US35855782A US4454112A US 4454112 A US4454112 A US 4454112A US 35855782 A US35855782 A US 35855782A US 4454112 A US4454112 A US 4454112A
Authority
US
United States
Prior art keywords
tocopherol
acetylsalicylate
skin
composition containing
present
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US06/358,557
Inventor
Francis W. Tuominen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel Corp
Original Assignee
Henkel Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Corp filed Critical Henkel Corp
Priority to US06/358,557 priority Critical patent/US4454112A/en
Assigned to HENKEL CORPORATION A CORP OF DE reassignment HENKEL CORPORATION A CORP OF DE ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: TUOMINEN, FRANCIS W.
Application granted granted Critical
Publication of US4454112A publication Critical patent/US4454112A/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
    • A61K8/498—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom having 6-membered rings or their condensed derivatives, e.g. coumarin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
    • A61K8/368—Carboxylic acids; Salts or anhydrides thereof with carboxyl groups directly bound to carbon atoms of aromatic rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/67—Vitamins
    • A61K8/678—Tocopherol, i.e. vitamin E
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations

Definitions

  • the present invention describes the formation and use of esters containing a tocopherol (particularly Vitamin E) and a acetylsalicyclic acid structure.
  • Water soluble tocopherol derivatives prepared by esterifying tocopherol acid esters with polyethylene glycol are described in U.S. Pat. No. 2,680,749 to Cawley et al. on June 8, 1954.
  • tocopherol acid esters described by Cawley as suitable for condensation with the polyethylene glycol include: succinates, citraconates, methyl citraconates, itaconates maleates, glutaconates, and phthalates.
  • tocopherol ascorbates The preparation of tocopherol ascorbates is described by Spanel in U.S. Pat. No. 3,151,127 issued Sept. 29, 1964.
  • U.S. Pat. No. 3,869,477 issued Mar. 4, 1975 to Schindo et al. describes the preparation of tocopherol-p-chlorophenoxyisobutyric acid esters which are stated to have an affect on arteriosclerosis and of affecting betterment of lipid metabolism.
  • Vitamin A acid esters of tocopherol are described in U.S. Pat. No. 3,878,202 issued Apr. 15, 1975 to Fukawa et al. Cholesterol esters of acetylsalicylate were stated to have been prepared by Montignie in the Bull. soc. chim. 49, 1852-1853 (1931).
  • the present invention is concerned with tocopherol acetylsalicylate as novel compounds.
  • the tocopherol acetylsalicylate is alpha-tocopherol orthoacetylsalicylate.
  • the tocopherol acetylsalicylates described herein have been found useful as sunscreening agents in that the subject compounds absorb ultraviolet light.
  • the present compounds also have utility in that oral administration of the compounds will provide sustained release of acetylsalicyclic acid in mammals.
  • the present invention as previously stated relates to the preparation of tocopherol acetylsalicylates.
  • the preferred form of tocopherol is that commonly denominated as alpha-tocopherol.
  • the alpha-tocopherol may be either natural or synthetically produced.
  • Other tocopherols may also be used in the present invention including the beta, gamma, and delta forms.
  • the acetylsalicylate portion of the novel ester is conveniently provided by an acetylsalicyloyl halide in particular, acetylsalicyloyl chloride.
  • the preferred structure for the acetylsalicylate is that of the ortho isomer.
  • the preparation of the tocopherol acetylsalicylate is conveniently carried out by reacting equal molar quantities of the tocopherol and acetylsalicyloyl chloride using toluene as a solvent. While the reaction to the tocopherol and the acetylsalicyloyl chloride is conveniently carried out on an equal molar basis, it is also possible to include excess amounts of one ingredient or the other to ensure completion of the reaction. Thus it is often desirable to include a slight excess of the acetylsalicyloyl chloride due to the fact that the tocopherol is the more expensive reactant.
  • dimethyl aniline is added to the reaction mixture to function as a hydrogen chloride scavenger.
  • the dimethyl aniline may be added in a slight molar excess to the amount of hydrogen chloride which forms during the reaction.
  • the dimethyl aniline hydrochloride so formed is extracted with sufficient water to ensure its removal.
  • the tocopherol acetylsalicylate in the toluene solution is then treated with a drying agent such as calcium sulfate to remove the water.
  • a drying agent such as calcium sulfate to remove the water.
  • the drying agent is then filtered out of the mixture of toluene and product.
  • the toluene is then distilled off using reduced pressure and a temperature of about 50 degrees Celsius.
  • the residue is then purified by trituration with acetonitrile to remove any unreacted materials. Any excess acetonitrile is then removed from the reaction product at slightly reduced pressure.
  • the tocopherol acetylsalicylate may be further purified by successive triturations using the acetonitrile until the tocopherol acetylsalicylate reaches the desired degree of purity. It will be recognized that the degree of purity for oral usage should be higher than that for its topical use as a sunscreen.
  • the compounds of the present invention as previously stated, have two beneficial uses.
  • the first use is that of the compound as a sunscreening agent to absorb a selected portion of the ultraviolet spectrum.
  • the compounds of the present invention may be utilized in medicinal preparation as a sustained release agent of acetylsalicylate ions or aspirin.
  • the tocopherol acetylsalicylate is found to absorb ultraviolet radiation having a maximum absorbence at 288 nanometers. At one-half of the absorbtion maximum the wave lengths at which the compound is absorbing ultraviolet radiation is from 265 to 310 nanometers.
  • the compositions of the present invention are thus useful in absorbing a portion of the intense ultraviolet radiation at the specified wavel lengths. That is, it must be remembered that the purpose of any sunscreening agent (UV absorber) is not to prevent the suns ultraviolet radiation from reaching the skin, but to reduce its intensity so as to enable the skin to build up its own protection against exposure by means of tanning.
  • ultraviolet radiation has the ability to induce skin carcinoma over a substantial portion of the ultraviolet spectrum. It is thus suggested that the use of the tocopherol acetylsalicylate protects the skin from overdoses of ultraviolet radiation within the aforementioned wave length band.
  • tocopherol acetylsalicylate as a sunscreen that there are purported effects of the use of tocopherols as skin conditioning agents. That is, the use of tocopherol and in particular alpha-tocopherol, that the skin retains a youthful appearance for a longer period of time than skin not so treated. This is particularly important when considering that the tocopherol acetylsalicylates of the present invention are suggested for use under adverse climatic conditions. That is the compounds of the present invention when used as a sunscreen, not withstanding the effect of absorbing ultraviolet light, should provide skin care benefits due to the tocopherol portion of the molecule. Additionally, the tocopherol acetylsalicylate is not readily washed away from the skin and thus repeated applications of a sunscreen formulation containing the tocopherol acetylsalicylate are not frequently needed during sunbathing.
  • the desired effect of the second suggested utility for the tocopherol acetylsalicylate lies primarily in the fact that it has been widely reported that ordinary aspirin causes gastrointestinal irritation and bleeding, thus causing or aggravating ulcerated conditions. It is believed that when aspirin in its conventional form is taken orally that is dissolves in the stomach presenting concentrated areas of acetylsalicylic acid in the gastrointestinal environment. A solution of this problem of stomach irritation is to present the aspirin in such a form that it is slowly hydrolyzed to the active acid.
  • the effect of introducing the acetylsalycilic acid in the form of tocopherol acetylsalicylate is to yield a sustained release of the acetylsalicylate in the stomach or the blood. Slow release, followed by uptake in the blood of the tocopherol acetylsalicylate minimizes the concentration in the stomach of the acid form.
  • the dosage required of the tocopherol acetylsalicylate is simply a molar extension of that used in conventional aspirin products. Preparation of this aspirin substitute would follow conventional aspirin products with the exception of using the ester of the present invention.
  • tocopherol acetylsalicylate could be introduced into the patient by injection.
  • the formation of the alpha-tocopherol orthoacetylsalicylate is carried out by refluxing the mixture described above for a period of one hour. At the end of one hour the reaction is essentially complete and the dimethyl aniline hydrochloride formed during the reaction is removed by water extraction. The water extraction is carried out by using three successive 200 milliliter washes in a separatory funnel. The non-aqueous phase containing the toluene and the alpha-tocopherol orthoacetylsalicylate is retained and dried with calcium sulphate to remove any water remaining.
  • reaction mixture following the drying steps described above is then filtered in a Buchner funnel to remove the calcium sulphate.
  • the toluene is then removed by vacuum distillation using an aspirator.
  • the mixture obtained following removal of the toluene is a light brown oily liquid.
  • This residue is then triturated with acetonitrile to remove any unreacted tocopherol.
  • the amount of acetonitrile utilized is about 10 milliliters per gram of residue.
  • the product may be further purified if desired by successive triturations of the tocopherol acetylsalicylate with acetonitrile. In most cases the additional trituration technique is unnecessary.
  • Example I The product of Example I is formulated in a sunscreen lotion having the following composition:
  • the foregoing formulation is found effective in reducing the amount of ultraviolet radiation reaching the skin when applied at a level of 0.25 grams per square centimeter of skin surface.
  • the wave length of the ultraviolet radiation absorbed by the composition is determined to have an absorption maximum at 288 nanometers and a band width at one-half of the absorbtion maximum of 45 nanometers.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Emergency Medicine (AREA)
  • Dermatology (AREA)
  • Cosmetics (AREA)

Abstract

The present invention describes the preparation and utilization of tocopherol acetylsalicylate compounds which have utility for lessening erythema.

Description

This is a continuation of application Ser. No. 865,081, filed Dec. 27, 1977, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention describes the formation and use of esters containing a tocopherol (particularly Vitamin E) and a acetylsalicyclic acid structure.
2. Description of the Art
Various tocopherol derivatives are known to exist. For instance U.S. Pat. No. 2,231,125 issued to Karrer on Feb. 11, 1941 describes the preparation of stearic and oleic esters of tocopherol. Karrer discusses the introduction of allyl groups into tocopherol in U.S. Pat. No. 2,245,480 issued June 10, 1941.
The preparation of tocopherol succinates by Baxter et al. is found in U.S. Pat. No. 2,358,046 issued Sept. 22, 1944. The preparation of crystalline dl-alpha-tocopheral-p-nitro-benzoic acid esters is described in U.S. Pat. No. 2,393,134 issued to Aeschlimann Jan. 15, 1946. The process of esterifying tocopherols with acyl halides is set out in U.S. Pat. No. 2,486,541 issued to Baxter et al. on Nov. 1, 1949.
Water soluble tocopherol derivatives prepared by esterifying tocopherol acid esters with polyethylene glycol are described in U.S. Pat. No. 2,680,749 to Cawley et al. on June 8, 1954. Among the tocopherol acid esters described by Cawley as suitable for condensation with the polyethylene glycol include: succinates, citraconates, methyl citraconates, itaconates maleates, glutaconates, and phthalates.
The preparation of tocopherol ascorbates is described by Spanel in U.S. Pat. No. 3,151,127 issued Sept. 29, 1964. U.S. Pat. No. 3,869,477 issued Mar. 4, 1975 to Schindo et al. describes the preparation of tocopherol-p-chlorophenoxyisobutyric acid esters which are stated to have an affect on arteriosclerosis and of affecting betterment of lipid metabolism. Vitamin A acid esters of tocopherol are described in U.S. Pat. No. 3,878,202 issued Apr. 15, 1975 to Fukawa et al. Cholesterol esters of acetylsalicylate were stated to have been prepared by Montignie in the Bull. soc. chim. 49, 1852-1853 (1931).
To date, other researchers have not explored the utilization and preparation of tocopherol acetylsalicylates. Throughout the specification and claims percentages and ratios are by weight and temperatures are in degrees Celsius, unless otherwise indicated.
SUMMARY OF THE INVENTION
The present invention is concerned with tocopherol acetylsalicylate as novel compounds. Most preferably the tocopherol acetylsalicylate is alpha-tocopherol orthoacetylsalicylate.
The tocopherol acetylsalicylates described herein have been found useful as sunscreening agents in that the subject compounds absorb ultraviolet light. The present compounds also have utility in that oral administration of the compounds will provide sustained release of acetylsalicyclic acid in mammals.
DETAILED DESCRIPTION OF THE INVENTION
The present invention as previously stated relates to the preparation of tocopherol acetylsalicylates. The preferred form of tocopherol is that commonly denominated as alpha-tocopherol. The alpha-tocopherol may be either natural or synthetically produced. Other tocopherols may also be used in the present invention including the beta, gamma, and delta forms.
The acetylsalicylate portion of the novel ester is conveniently provided by an acetylsalicyloyl halide in particular, acetylsalicyloyl chloride. The preferred structure for the acetylsalicylate is that of the ortho isomer.
The preparation of the tocopherol acetylsalicylate is conveniently carried out by reacting equal molar quantities of the tocopherol and acetylsalicyloyl chloride using toluene as a solvent. While the reaction to the tocopherol and the acetylsalicyloyl chloride is conveniently carried out on an equal molar basis, it is also possible to include excess amounts of one ingredient or the other to ensure completion of the reaction. Thus it is often desirable to include a slight excess of the acetylsalicyloyl chloride due to the fact that the tocopherol is the more expensive reactant.
To further facilitate completion of the reaction of the tocopherol and the acetylsalicyloyl chloride, dimethyl aniline is added to the reaction mixture to function as a hydrogen chloride scavenger. The dimethyl aniline may be added in a slight molar excess to the amount of hydrogen chloride which forms during the reaction. The dimethyl aniline hydrochloride so formed is extracted with sufficient water to ensure its removal.
The tocopherol acetylsalicylate in the toluene solution is then treated with a drying agent such as calcium sulfate to remove the water. The drying agent is then filtered out of the mixture of toluene and product. The toluene is then distilled off using reduced pressure and a temperature of about 50 degrees Celsius. The residue is then purified by trituration with acetonitrile to remove any unreacted materials. Any excess acetonitrile is then removed from the reaction product at slightly reduced pressure.
The tocopherol acetylsalicylate may be further purified by successive triturations using the acetonitrile until the tocopherol acetylsalicylate reaches the desired degree of purity. It will be recognized that the degree of purity for oral usage should be higher than that for its topical use as a sunscreen.
The compounds of the present invention as previously stated, have two beneficial uses. The first use is that of the compound as a sunscreening agent to absorb a selected portion of the ultraviolet spectrum. Secondly, the compounds of the present invention may be utilized in medicinal preparation as a sustained release agent of acetylsalicylate ions or aspirin.
In the first utility of the present invention, namely that of ultraviolet absorption, the tocopherol acetylsalicylate is found to absorb ultraviolet radiation having a maximum absorbence at 288 nanometers. At one-half of the absorbtion maximum the wave lengths at which the compound is absorbing ultraviolet radiation is from 265 to 310 nanometers. The compositions of the present invention are thus useful in absorbing a portion of the intense ultraviolet radiation at the specified wavel lengths. That is, it must be remembered that the purpose of any sunscreening agent (UV absorber) is not to prevent the suns ultraviolet radiation from reaching the skin, but to reduce its intensity so as to enable the skin to build up its own protection against exposure by means of tanning. Moreover, it has been suggested that ultraviolet radiation has the ability to induce skin carcinoma over a substantial portion of the ultraviolet spectrum. It is thus suggested that the use of the tocopherol acetylsalicylate protects the skin from overdoses of ultraviolet radiation within the aforementioned wave length band.
It has also been noted with respect to the use of the tocopherol acetylsalicylate as a sunscreen that there are purported effects of the use of tocopherols as skin conditioning agents. That is, the use of tocopherol and in particular alpha-tocopherol, that the skin retains a youthful appearance for a longer period of time than skin not so treated. This is particularly important when considering that the tocopherol acetylsalicylates of the present invention are suggested for use under adverse climatic conditions. That is the compounds of the present invention when used as a sunscreen, not withstanding the effect of absorbing ultraviolet light, should provide skin care benefits due to the tocopherol portion of the molecule. Additionally, the tocopherol acetylsalicylate is not readily washed away from the skin and thus repeated applications of a sunscreen formulation containing the tocopherol acetylsalicylate are not frequently needed during sunbathing.
The desired effect of the second suggested utility for the tocopherol acetylsalicylate lies primarily in the fact that it has been widely reported that ordinary aspirin causes gastrointestinal irritation and bleeding, thus causing or aggravating ulcerated conditions. It is believed that when aspirin in its conventional form is taken orally that is dissolves in the stomach presenting concentrated areas of acetylsalicylic acid in the gastrointestinal environment. A solution of this problem of stomach irritation is to present the aspirin in such a form that it is slowly hydrolyzed to the active acid. The effect of introducing the acetylsalycilic acid in the form of tocopherol acetylsalicylate is to yield a sustained release of the acetylsalicylate in the stomach or the blood. Slow release, followed by uptake in the blood of the tocopherol acetylsalicylate minimizes the concentration in the stomach of the acid form. The dosage required of the tocopherol acetylsalicylate is simply a molar extension of that used in conventional aspirin products. Preparation of this aspirin substitute would follow conventional aspirin products with the exception of using the ester of the present invention.
Additionally, it must be remembered when using a biologically active form of tocopherol acetylsalicylate that not only will the aspirin be made available for medicinal purposes, but that the tocopherol will also be available as Vitamin E or a precursor thereof. Thus another distinct advantage of the present invention is that patients requiring both aspirin and Vitamin E supplementation in the diet will only need to take one form of medication as opposed to successive treatments. It will also be recognized that tocopherol acetylsalicylate could be introduced into the patient by injection.
The following are examples related to the present invention:
EXAMPLE I Preparation of Alpha-Tocopherol Orthoacetylsalicylate
50 grams of alpha-tocopherol and 25 milliliters of ortho acetylsalicyloyl chloride are added to a flask utilizing 400 milliliters of toluene as a solvent. The reaction flask and the toluene were previously dried to remove any moisture present in the system. To the reaction mixture 23 milliliters of dimethyl aniline is added to scavenge the hydrogen chloride liberated during the esterification.
The formation of the alpha-tocopherol orthoacetylsalicylate is carried out by refluxing the mixture described above for a period of one hour. At the end of one hour the reaction is essentially complete and the dimethyl aniline hydrochloride formed during the reaction is removed by water extraction. The water extraction is carried out by using three successive 200 milliliter washes in a separatory funnel. The non-aqueous phase containing the toluene and the alpha-tocopherol orthoacetylsalicylate is retained and dried with calcium sulphate to remove any water remaining.
The reaction mixture following the drying steps described above is then filtered in a Buchner funnel to remove the calcium sulphate. The toluene is then removed by vacuum distillation using an aspirator. The mixture obtained following removal of the toluene is a light brown oily liquid. This residue is then triturated with acetonitrile to remove any unreacted tocopherol. The amount of acetonitrile utilized is about 10 milliliters per gram of residue.
Following removal of the excess acetonitrile and the by-products of the reaction, 41 grams of a mixture containing the alpha-tocopherol acetylsalicylate are obtained. The purity of the desired reaction product is greater than 90%. The remaining impurity is largely acetylsalicylic acid which is not at all undesirable in the orally administered products as it may be neutralized and left in the dosage. That is the end product may be prepared to comprise both a large portion of the tocopherol acetylsalicylate for delayed release and a smaller amount of readily accessible aspirin for fast relief.
The product may be further purified if desired by successive triturations of the tocopherol acetylsalicylate with acetonitrile. In most cases the additional trituration technique is unnecessary.
Similar products may be prepared and utilized in the succeeding examples from beta, gamma, and delta tocopherols.
EXAMPLE II Utilization of the Alpha-Tocopherol Orthoacetylsalicylate
The product of Example I is formulated in a sunscreen lotion having the following composition:
alpha-tocopherol orthoacetylsalicylate 1%
oleyl alcohol 10%
mineral oil 89%
The foregoing formulation is found effective in reducing the amount of ultraviolet radiation reaching the skin when applied at a level of 0.25 grams per square centimeter of skin surface. The wave length of the ultraviolet radiation absorbed by the composition is determined to have an absorption maximum at 288 nanometers and a band width at one-half of the absorbtion maximum of 45 nanometers.

Claims (2)

What is claimed is:
1. A method of reducing the amount of ultraviolet radiation receiving the skin which includes contacting the skin with an effective amount of tocopherol acetylsalicylate to reduce the amount of the ultraviolet radiation reaching the skin.
2. A sunscreen composition containing 1% tocopherol acetylsalicylate, 10% oleyl alcohol, and 89% mineral oil.
US06/358,557 1977-12-27 1982-03-16 Sunscreen composition containing tocopherol acetylsalicylate Expired - Fee Related US4454112A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US06/358,557 US4454112A (en) 1977-12-27 1982-03-16 Sunscreen composition containing tocopherol acetylsalicylate

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US86508177A 1977-12-27 1977-12-27
US06/358,557 US4454112A (en) 1977-12-27 1982-03-16 Sunscreen composition containing tocopherol acetylsalicylate

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US86508177A Continuation 1977-12-27 1977-12-27

Publications (1)

Publication Number Publication Date
US4454112A true US4454112A (en) 1984-06-12

Family

ID=27000106

Family Applications (1)

Application Number Title Priority Date Filing Date
US06/358,557 Expired - Fee Related US4454112A (en) 1977-12-27 1982-03-16 Sunscreen composition containing tocopherol acetylsalicylate

Country Status (1)

Country Link
US (1) US4454112A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0166221A3 (en) * 1984-05-29 1987-06-03 Henkel Corporation Sunscreen composition and method of use
US5192534A (en) * 1988-12-30 1993-03-09 L'oreal Composition for inducing and stimulating hair growth and/or retarding its loss, based on pyrimidine derivatives and sunscreens
DE4333794A1 (en) * 1993-10-04 1995-04-06 Carl Heinrich Dr Weischer Acetylsalicylic acid derivatives for controlling states of inflammation and pain and for the prophylaxis and therapy of thrombosis
EP0775488A1 (en) 1995-11-23 1997-05-28 Mazal Pharmaceutique Stable pharmaceutical composition on the basis of acetylsalicyclic acid and tocopherol
US5643554A (en) * 1993-04-30 1997-07-01 Dusa Pharmaceuticals, Inc. Lipomelanim composition
US5662894A (en) * 1993-08-03 1997-09-02 Mcmanus; Jt Sunshield shaving compositions
US6036946A (en) * 1997-12-24 2000-03-14 Shaklee Corporation Methods for protecting skin from damaging effects of ultraviolet light
US6146664A (en) * 1998-07-10 2000-11-14 Shaklee Corporation Stable topical ascorbic acid compositions

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3177120A (en) * 1960-06-01 1965-04-06 Plough Stable cosmetic preparations containing dihydroxy acetone
FR2314722A1 (en) * 1975-06-19 1977-01-14 Etud Expl Marques Brevets Tocopheryl acetyl-salicylates and analogues - with antithrombotic activity, esp. in compsns. with acetyl-salicylates of papaverine or ethaverine
US4144325A (en) * 1976-11-10 1979-03-13 Voyt Walter F Method of and composition for preventing sunburn while affording tanning
US4154823A (en) * 1976-06-10 1979-05-15 Schutt Steven R Skin treatment compositions and methods of using same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3177120A (en) * 1960-06-01 1965-04-06 Plough Stable cosmetic preparations containing dihydroxy acetone
FR2314722A1 (en) * 1975-06-19 1977-01-14 Etud Expl Marques Brevets Tocopheryl acetyl-salicylates and analogues - with antithrombotic activity, esp. in compsns. with acetyl-salicylates of papaverine or ethaverine
US4154823A (en) * 1976-06-10 1979-05-15 Schutt Steven R Skin treatment compositions and methods of using same
US4144325A (en) * 1976-11-10 1979-03-13 Voyt Walter F Method of and composition for preventing sunburn while affording tanning

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Nakamura et al., Chem. Abstract, 76, 34105x, (1972). *
Nakamura et al., Chem. Abstract, 84, 25708j, (1976). *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0166221A3 (en) * 1984-05-29 1987-06-03 Henkel Corporation Sunscreen composition and method of use
AU576863B2 (en) * 1984-05-29 1988-09-08 Henkel Corporation Sunscreen composition containing tocopherol ester
US5192534A (en) * 1988-12-30 1993-03-09 L'oreal Composition for inducing and stimulating hair growth and/or retarding its loss, based on pyrimidine derivatives and sunscreens
US5643554A (en) * 1993-04-30 1997-07-01 Dusa Pharmaceuticals, Inc. Lipomelanim composition
US5750093A (en) * 1993-04-30 1998-05-12 Dusa Pharmaceuticals, Inc. 33 Lipomelanin sunscreen composition
US5662894A (en) * 1993-08-03 1997-09-02 Mcmanus; Jt Sunshield shaving compositions
DE4333794A1 (en) * 1993-10-04 1995-04-06 Carl Heinrich Dr Weischer Acetylsalicylic acid derivatives for controlling states of inflammation and pain and for the prophylaxis and therapy of thrombosis
EP0775488A1 (en) 1995-11-23 1997-05-28 Mazal Pharmaceutique Stable pharmaceutical composition on the basis of acetylsalicyclic acid and tocopherol
US6036946A (en) * 1997-12-24 2000-03-14 Shaklee Corporation Methods for protecting skin from damaging effects of ultraviolet light
US6174519B1 (en) 1997-12-24 2001-01-16 Shaklee Corporation Composition for protecting skin from damaging effects of ultraviolet light
US6146664A (en) * 1998-07-10 2000-11-14 Shaklee Corporation Stable topical ascorbic acid compositions

Similar Documents

Publication Publication Date Title
US4610978A (en) Compositions containing 1α-hydroxycholecalciferol for topical treatment of skin disorders and methods employing same
US4216224A (en) Methods and compositions for treating psoriasis with retinoyl compounds
US4895839A (en) Pharmaceutical and cosmetic compositions containing complexes of flavanolignans with phospholipids
KR880007507A (en) Croman derivatives
US4978523A (en) Melanin inhibitor
US4454112A (en) Sunscreen composition containing tocopherol acetylsalicylate
US3326768A (en) Antiperspirant composition
EP0133437A1 (en) Vitamin-containing skin care ointment
CA1184498A (en) Compositions for treating acne
USRE33107E (en) Compositions containing 1α-hydroxycholecalciferol for topical treatment of skin disorders and methods employing same
EP0166221B1 (en) Sunscreen composition and method of use
EP0338565B1 (en) N-Alkoxyalkylamides of hydroxyacids and skin treating compositions therewith
JPS609722B2 (en) fair skin cosmetics
DE68919009T2 (en) Use of 5-amino-salicylic acid for the treatment of skin diseases.
US4764361A (en) Pharmaceutical compositions
US4602036A (en) Panthenol derivatives
CA1045629A (en) Allantoin ascorbic acid complex
US2974089A (en) Sun screen compositions
CA1253807A (en) Topical composition for the protection and treatment of human skin or hair
US3697642A (en) Method of protecting the skin from ultraviolet radiation with titanic acid and esters of titanic acid
JP3081030B2 (en) Skin whitening agent
CA1036941A (en) Anti-inflammatory preparation
IE47494B1 (en) An erythormycin compound,a process for preparing the compound and compositions containing the compound useful in the treatment of acne
US2213717A (en) Alkyl esters of 3-methoxy-coumaric acid and pharmaceutical compositions containing same
NO173278C (en) Analogous Process for Preparing Therapeutically Active 5-Androsten-17-one Derivatives

Legal Events

Date Code Title Description
AS Assignment

Owner name: HENKEL CORPORATION A CORP OF DE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:TUOMINEN, FRANCIS W.;REEL/FRAME:004240/0371

Effective date: 19840327

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
FP Lapsed due to failure to pay maintenance fee

Effective date: 19960612

STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362